Dye of the naphtho-phenazine series and process of making it



Patented May 9, 1933 OTTO ALLEMANN, on ILMINGTON, DELAWARE, hesitation Mai. be PONTHDE PATENT OFFICE NEMOURS & COMPANY, OF WILMINGTON, DELAWARE, A CORPORATION OF DELA- WARE DYE OF THE NAIHTHO-PHENAZINE SERIES AND PROCESS OF MAKING IT No Drawing.

This invention relates generally to organic compounds and specifically to compounds or dyes of the naphtho-phenazine series. More particularly it relates to new iso-rosindulines and new rosinduline compounds.

In the matter of prior art attention may be directed to German Patents 19,224 and 40,886, which disclose the preparation of isorosindulines from the paranitroso derivatives of tertiary amines. In addition, German Patents 97,118 and 97,365 describe the preparation of rosindulines from iso-rosindulines such as Neutral blue.

This invention has for an object the production of new organic compounds. More specifically the invention contemplates the preparation of a new series of iso-rosindulines and a new series of rosindulines. Other objects will appear hereinafter.

These objects are accomplished by the present invention whereby compounds of the following probable general formulae are produced: I

(KHz-(5E2 N N O I A R OH2- Ha (The iso-rosindulines) (The rosindulines) in which, R represents an alkyl or aryl group which may be substituted, R represents H or Applicatien filed August 15, 1930. Serial No. 475,631.

(Rosinduline) The invention will be further understood from a consideration of the following examples in which the parts are given by weight.

PKRT IIso-RosINnuLINns The reaction utilized probably takes place according to the following equation Ell l LN I I will 5 E g-6H2 Ewantple [I A mixture of 25 parts of para-tolyl-betanaphthylamine 45 parts of nitroso-phenylmorpholine hydrochlorideand 150 parts of methyl alcohol was treated the same way as indicated in Example I. The dye dyes cotton a blue shade. The dye has the following probable formula 7 following probable formula Example [I] i A mixture of 17.5 parts of ethyl-betanaphthylamine 45.0 parts of nitroso-phenyl- .morpholine hydrochloride and 150.0 parts of methyl alcohol was heated and the dye isolated according to directions in Example I. It dyes cotton a violet shade.

Emample I V A mixture of 16 parts of diphenyl-2z7- PART II-Rosmnonmns l Example V A mixture of 19 parts of an iso-rosinduline (from nitroso phenyl morpholine-l-ethylbeta-naphthylamine) and 16 parts of metatoluylene-diamine were dissolved in 150 parts of ethyl alcohol. 10 parts of caustic soda solution (85%) were then added and the oxidation effected bypassing a current of air through the solution at 40-45 C. The re action was finished when a drop of the solution dissolved in concentrated sulphuric acid with a grass green color. The alcohol was then distilled off and from the residue the dye extracted with hot dilute hydrochloric acid. From this solution the new rosinduline was salted out with salt. It dyed cotton a reddish-violet shade. The reaction probably The dye has the takes Example VI A mixture of 22 parts of an iso-rosinduline (from nitroso-phenyl-morpholine and para-tolyl-beta-naphthylamine), and 12 parts of. para-amido-diphenylamine were dissolved in 200 parts of ethyl alcohol. 12 parts of caustic soda solution (35%) were then added and a current of air passed through the solution at 40-45" C., until a drop of the solution dissolved in concentrated sulphuric acid with a green color. The rosinduline was filtered off and dried. Through sulphonation it can be converted into an acid dye which dyes wool a blue shade. The compound produced probably has the following formula Ewample VI! A mixture of 25 parts of an iso-rosinduline (from nitroso'phenyl-morpholine and .diphenyl-2 7 -naphthylene-diamine), and 10 parts of aniline were dissolved in ISOparts of ethyl alcohol. 12 parts of caustic soda solution (85%) were then added and a current of air passed through the solution at l550 0., until a drop of the solution dissolved in concentrated sulphuric acid with a green color. The rosinduline was then filtered off and dried. It may be sulphonated toan acid dye which dyes wool a blue shade,

The compound produced probably has the following formula Ewamplc V111 A mixture of 22 parts of an iso-rosinduline (from nitroso phenyl morpholine'tparaethozry-phenyl-beta-naphthylamine), and 10 pa of para-amino-dimethylaniline were dis. olved in 150 parts of ethyl alcohol. 12 parts of caustic soda solution (35%) were then added and oxidation carried out by passing a current of air through the solution at SS-40 Cu until a drop dissolved with green color in concentrated. sulphuric acid. The rosinduline was filtered off and dissolved in hot dilute hydrochloric acid. From this solution the dye was salted out with salt. It dyed cotton a violet shade. The compound prolduced probably has the following formu a Various modifications may be made within the scope of the invention.

Other solvents may replace the methyl alcohol used in the preparation of iso-rosindulines as set out above, for example, ethyl alcohol or acetic acid give satisfactory re sults.

The number 03'? compounds which are obviously adapted to yield dyes of both of the classes herein described is very large and consequently it is impractical to attempt to list them all.

Certain compounds merit special mention, however, for instance in the preparation of the iso-rosindulines in place of the phenylbeta naphthylaniine (Example 1), paratolyl-betaamplithylamine (Example lized in this invention.

and 'ethyl-beta-naphthylamine (Example 111) the following may be used with very desirable results: ortho-tolyl-beta-naphthylamine, Xylyl-beta-naphthylamine, methylbeta-naphthylamine, butyl-beta-naphthylamine, para-methoXy-phenyl-beta-naphthylamine, para-ethoXy-phenyl-beta naphthylamine, ortho-methoxy-phenyl-beta-naphthylam ine, ortho-ethoxy-phenyl-beta-naphthylamme.

Especially satisfactory results are obtained from the compounds formed by replacing the di-phenyl-2:7-naphthylene-diamine of Example IV with di-tolyl-2: 7- naphthylene di-amine, di-xylyl-2z7-naphthylene di-amine, para-methoXy-di-phenyl- 2:7-naphthylene di-amine, para-ethoXy-diphenyl-2 7 naphthylene di-amine, orthomethoxy diphenyl 2 7 naphthylene di amine, ortho-ethoXy-di-phenyl 2 7 naphthylene di-amine, or the corresponding derivatives of 2: 6 naphthylene di-amine.

" In the preparation of the rosindulines, in the place of meta-toluylene-di-amine (EX- ample V), para amido di phenylamine (Example VI), aniline (Example VII) and para-amido di methyl aniline (Example VIII), the following may be used with excellent results: toluidine, Xylidine, metaphenylene-di-amine, para amido methyl ethyl-aniline, para-amido-di-ethyl aniline, para-amido-phenyl-morpholine, para amido-methyl-benzyl-aniline, para-amido-ethylbenzyl-aniline.

Also the nitrated and sulphonated derivatives of primary amines such as sulphanilic acid, metanilic acid, para-amido-ethyl-benzyl-aniline-sulphonic acid, metaand paranitro-aniline may be used.

It is desired to emphasize the fact that applicant in the above list of specific compounds has not attempted to enumerate all compounds which may be successfully uti- On the contrary, certain outstanding compounds have been mentioned for purposes of illustrating the invention and without intent to limit it.

I While certain reactions, equations and theories have been set out above to aid in understanding the invention it is to be understood that it is not desired to limit the invention thereby.

' The iso-rosinduline compounds made according to the above described invention are suitable for dyeing cotton and acetyl silk.

The rosinduline compounds produced as above described are suitable for dyeing silk, cotton, acetyl silk and wool.

The new iso-rosinduline dyes of this invention difier in shades from the known dyes of this class. i

The new rosinduline dyes differ inshade from those. prepared with iso-rosindulines obtained from para-nitroso derivatives of dimethyl-aniline, methyl-ethyl-aniline, and

di-ethyl aniline in that they are somewhat redder and when used as basic dyes have more affinity for acetyl silk.

As many apparently widely different embodiments of this invention may be made without departing from the spirit and scope thereof, it is to be understood that I do not limit myself to the specific embodiments thereof except as defined in the appended claims. 7

I claim:

1. The compounds having the following probable general formula I l CHr-QH:

in which R represents an alkyl or phenyl group which may be substituted by a radical of the group consisting of alkyl and alkoXy, R represents H or and'R- represents an alkyl or phenyl group which may be substituted by a radical of the group consisting of alkyl and alkoxy.

2. The compound having the following probable general formula in which R represents an. alkyl or phenyl group which may be substituted by a member of the group consisting of alkyl and alkoxy, R represents H or Ill) 6. A basic iso-rosinduline dye containing a morpholine radical in the 3 position.

7. An acid iso-rosinduline dye containing a morpholine radical in the 3 position.

8. A basic rosinduline dye containing a morpholine nucleus in the 3 position.

9. An acid rosinduline dye containing a morpholine nucleus in the 3 position.

10. The process comprising condensing an iso-rosinduline compound containing a morpholine nucleus in the 3 position with a primary amine.

11. The process comprising condensing para-nitroso-phenyl-morpholine hydrochloride with a secondary derivative of betanaphthylamine of the group consisting of alkyl, phenyl, alkyl-phenyl and alkoxyphenyl. i

12. The process comprising condensing para-nitroso-phenyl-morphoiine hydrochloride With a secondary derivative of betanaphthylamine of the group consisting of methyl, ethyl butyl, phenyl, tolyl xylyl, anisidyl and phenetidyl.

13. The dye having the probable formula which is obtainable by reacting phenyLbetanaphthylamine and nitroso-phenyl-morpholine-hydrochloride and which dyes cotton a blue shade.

14. The dye having the probable formula H lz a SOaNa which is obtainable by reacting ortho-tolylbeta-naphthylamine with nitroso-phenylmorpholinehydrochloride, reacting the resultant with para-amido-ethyl-benzyl-aniline and sulphonating the product and which dyes wool blue shades of good fastness.

15. The process which comprises condensing para-nitroso-phenyl-morpholine-hydrochloride with a compound having the following general formula:

R represents a phenyl group which may be substituted by a member of the group consistin of alkyl and alkoXy.

16. The process which comprises reacting a compound having the following general formula:

with a compound having the following general formula 11 Rr-N in which R represents an alkyl or phenyl group which maybe substituted by a member of the group consisting of alkyl and alkoxy, R represents H or IEII R represents a phenyl group which may be substituted by a member of the group consisting of alkyl and allroxy, and R represents a phenyl group which may be substituted by a member of the group consisting of alkyl,

amino, alkyl-a1nino,nitro, sulfo, and morpl1oline.

17. The compound having the following general formula R (lH2 CH2 in which R represents an alkyl or phenyl group which may be susbstituted by a member of the group consisting of alkyl and a1- koxy, R represents H or R represents a phenyl group which may be substituted by a member of the group consisting of alkyl and alkoxy, and R represents a phenyl group which may be substituted by 0 a member of the group consisting of alkyl,

amino, a1ky1-amin0,nitr0, sulfo, and morpholine. I

' In testimony whereof, I aflix my signature.

,. OTTO ALLEMANN. 

